A compound with severely distorted geometry at ligated carbon: synthesis and x-ray crystal structure of Bi[CH(SiMe3)2]3, a trialkylbismuth complex with high thermal stability

(2,6-Mes2H3C6)2BiH, a Stable, Molecular Hydride of a Main Group Element of the Sixth Period, and Its Conversion to the Dibismuthene (2,6-Mes2H3C6)BiBi(2,6-Mes2C6H3)

“…The development of methods for the stereoselective formation of carbon ± carbon double bonds could be considered one of the most important challenges in organic synthesis. [1] The synthesis of a,b-unsaturated esters [2] is generally achieved by CC bond formation with Wittig, [3] Horner ± Emmons, [4] Heck, [5] or Peterson [6] reactions, or with the Cope rearrangement, [7] from acetylenic compounds [8] or a-sulfanylester derivatives. [9] However, in most of these papers, total control of the stereoselectivity of the carbon ± carbon double bond formation remained unresolved.…”

“…ca. 2.28, 2.328(13), and 2.357 (14) in the crowded molecules BiMes 3 [5] , Bi[CH(SiMe 3 ) 2 ] 3 [6] and Bi[2,4,6-Ph 3 C 6 H 2 ] 3 [7] ) and the C(1)-Bi-C(25) angle (123.9(3)8) is very wide in comparison to the usual angles seen in trivalent bismuth comon an Enraf-Nonius CAD4 diffractometer with Cu Ka radiation, 6856 of which were independent and used for all calculations. The structure was solved by direct methods (SHELXS-86 [11] ) and refined to F 2 anisotropically, the H atoms were refined with a riding model (SHELXL-93 [12] ).…”

New Approach to the ALD of Bismuth Silicates; Bi(CH2SiMe3)3 Acting as a Precursor for both Bismuth and Silicon

“…2.328(13) and 102.9(5), respectively observed for Bi(CH(SiMe 3 ) 2 ) 3 . [24] This observation is expected because (SiMe 3 ) 2 CH ± is sterically more demanding than (SiMe 3 )CH 2 ± . The Bi(1)±C (1)±Si (1) angle is 113.4(4).…”

Synthese und Einkristallröntgenstrukturanalyse von Bromdi(isopropenyl)bismutan

“…Bisher sind nur wenige Einkristallro È ntgenstrukturbestimmungen von aliphatischen Organobismutverbindungen bekannt [3,4,5] und noch keine von einem aliphatischen Di(organyl)-halogenbismutan. Im Hinblick auf eine mo È gliche Verwendung von Halogenbismutanen als Synthesebausteine fu È r organometallische Makromoleku È le [6 a, 6 b] interessierte uns besonders die Darstellung von Bromdi(isopropenyl)bismutan (2).…”

“…Dibrom(isopropenyl)-bismutan wurde bereits 1963 durch Reaktion von Tri(isopropenyl)bismutan mit Brom dargestellt [7]. Charakteristisch fu È r alle Verbindungen der dreiwertigen Elemente As, Sb, und Bi sind deren r-Donor-und p-Akzeptoreigenschaften, die sie nicht nur zu interessanten Komplexliganden machen [8,9,10], sondern auch der Anlaû dafu È r sind, daû in den Kristallstrukturen halogen-, sauerstoff-oder stickstoffhaltiger Derivate dieser Elemente ha È ufig intermolekulare Bru È ckenbindungen vorliegen [3,4,9,11,12,13]. Ausnahmen bilden Verbindungen, die sterisch anspruchsvolle Liganden enthalten und durch intramolekulare Koordination stabilisiert sind [14].…”